Background of the Invention
[0001] U. S. Patent No. 4,971,932 (Alpha et al.) is generally related to the construction
of magnetic memory storage devices, the essential components of which are a head pad
and a rigid information disc. As is described in that patent, the information disc
consists of two basic elements: (a) a rigid substrate, and (b) a coating of magnetic
media on the surface of the substrate facing the head pad. The disclosure of that
patent is directed specifically to the composition and structure of the rigid substrate.
[0002] Thus, the inventive concept encompassed within the patent comprised the fabrication
of the substrate from two different groups of glass-ceramic materials:
(1) glass-ceramics wherein crystals exhibiting a sheet silicate structure constitute
the predominant crystal phase; and
(2) glass-ceramics wherein crystals exhibiting a chain silicate structure constitute
the predominant crystal phase.
[0003] The patent cited seven characteristics of those glass-ceramics which rendered them
especially suitable for high performance rigid disc substrates:
(a) high body strengths and fracture toughnesses, as evidenced by moduli of rupture
between about 15,000-40,000psi (∼105-280 MPa) and KIC values between about 3-5 MPa√m, respectively;
(b) an elastic modulus at least equal to, and preferably higher than that of aluminum
metal (nickel phosphorus plated aluminum substrates have been used extensively in
information discs) such that the material is dimensionally stable at all thicknesses
and rotational velocities;
(c) a high surface hardness to impart excellent scratch resistance;
(d) the capability of forming precision surfaces (flat and smooth);
(e) a linear coefficient of thermal expansion between about 75-125x10⁻⁷/°C over the
temperature range of 25°-300°C;
(f) excellent resistance to attack in moist environments; and
(g) an inherently textured surface of a desired roughness (Ra=0.5-5nm) for enhanced magnetics and lower flying height.
[0004] As was disclosed in Patent No. 4,971,932, two composition areas within the general
system yielding glass-ceramics containing synthetic fluormica crystals with sheet
silicate structures have been investigated for their utility as substrates in rigid
information discs: (a) compositions wherein fluorophlogopite solid solution comprises
the predominant crystal phase, and (b) compositions wherein tetrasilicic fluormica
constitutes the predominant crystal phase.
[0005] U. S. Patent No. 3,689,293 (Beall) discloses the preparation of glass-ceramic articles
wherein fluorophlogopite solid solution comprises the predominant crystal phase, those
articles being suitable for the fabrication of substrates for rigid information discs.
Those glass-ceramics consist essentially, expressed in terms of weight percent on
the oxide basis, of:
| SiO₂ |
25-60 |
Cs₂O |
0-20 |
| B₂O₃ |
5-15 |
Na₂O+K₂O+Rb₂O+Cs₂O |
2-20 |
| Al₂O₃ |
5-25 |
MgO |
4-25 |
| B₂O₃+Al₂O₃ |
15-35 |
Li₂O |
0-7 |
| Na₂O |
0-15 |
MgO+Li₂O |
6-25 |
| K₂O |
0-15 |
F |
4-20 |
| Rb₂O |
0-15 |
|
|
[0006] One glass-ceramic having a composition coming within the above ranges which has been
found useful for forming substrates for rigid information discs is a product marketed
commercially by Corning Incorporated, Corning, New York as Corning 9658 under the
trademark MACOR. That glass-ceramic has the following approximate composition (O=F
is the oxygen ≃ fluoride correction factor):
| SiO₂ |
47.0 |
K₂O |
9.5 |
| B₂O₃ |
8.5 |
F |
6.3 |
| Al₂O₃ |
16.7 |
O=F |
2.5 |
| MgO |
14.5 |
|
|
[0007] U. S. Patent No. 3,732,087 (Grossman) discloses the preparation of glass-ceramic
articles wherein tetrasilicic fluormica comprises the predominant crystal phase, those
articles also being suitable for the formation of substrates for rigid information
discs. Those glass-ceramics consist essentially, expressed in terms of weight percent
on the oxide basis, of 45-70% SiO₂, 8-20% MgO, 8-15% MgF₂, 5-25% R₂O, wherein R₂O
consists of 0-20% K₂O, 0-20% Rb₂O, and 0-20% Cs₂O, 0-20% RO, wherein RO consists of
0-20% SrO, 0-20% BaO, and 0-20% CdO, and 5-35% R₂O+RO.
[0008] The preparation of substrates for rigid information discs from glass-ceramics containing
a chain silicate as the predominant crystal phase has been preferred, however, and
of such glass-ceramics three specifically-defined composition areas have been found
to be particularly effective:
(1) glass-ceramics wherein canasite constitutes the predominant crystal phase;
(2) glass-ceramics wherein potassium fluorrichterite constitutes the predominant crystal
phase; and
(3) glass-ceramics wherein potassium fluorrichterite constitutes the predominant crystal
phase, but wherein a substantial amount of cristobalite is also present.
[0009] Thus, highly crystalline glass-ceramics consisting of randomly-oriented, tightly
interlocked, high aspect ratio crystals of canasite or fluorrichterite are produced
by means of the controlled nucleation and crystallization of precursor glasses of
predetermined compositions. It is the crystalline microstructure of these glass-ceramics
which imparts the very high strength and toughness thereto, as well as a surface texture
of desirable roughness.
[0010] U. S. Patent No. 4,386,162 (Beall) describes the formation of glass-ceramic bodies
containing canasite and/or agrellite and/or fedorite as the predominant crystal phase.
Glass-ceramics satisfying the seven criteria set forth above for substrates of rigid
information discs have been prepared via heat treatment of parent glass bodies having
the following compositions, expressed in terms of weight percent on the oxide basis,
yielding articles wherein canasite comprises the predominant crystal phase:
| SiO₂ |
50-70 |
F |
4-9 |
| CaO |
15-25 |
MgO |
0-2 |
| Na₂O |
6-10 |
ZnO |
0-2 |
| K₂O |
6-12 |
SnO₂ |
0-2 |
| Al₂O₃ |
1-4 |
Sb₂O₃ |
0-1 |
[0011] U. S. Patent No. 4,467,039 (Beall et al.) discloses glass-ceramics wherein potassium
fluorrichterite constitutes the predominant crystal phase. Glass-ceramics encompassed
within that disclosure satisfying the above criteria have been produced through heat
treating glass articles having compositions within the intervals below, expressed
in terms of weight percent on the oxide basis, to form articles wherein potassium
fluorrichterite comprises essentially the sole crystal phase:
| SiO₂ |
58-70 |
K₂O |
3.8-7 |
| Al₂O₃ |
0.5-3 |
Li₂O |
0.5-2 |
| MgO |
13-17.5 |
BaO |
0-2.5 |
| CaO |
3-7 |
P₂O₅ |
0-2.5 |
| Na₂O |
1.5-4 |
F |
3-5.5 |
[0012] U. S. Patent No. 4,608,348 (Beall et al.) discusses glass-ceramics containing potassium
fluorrichterite as the predominant crystal phase, but which also contain at least
10% of cristobalite crystallization. Glass-ceramics included within that disclosure
satisfying the above criteria have been developed through the heat treatment of precursor
glass articles having the compositions recited below, expressed in terms of weight
percent on the oxide basis, of:
| SiO₂ |
65-69 |
K₂O |
4.2-6 |
| Al₂O₃ |
0.75-3 |
Li₂O |
0.5-2 |
| MgO |
13.5-16.5 |
BaO |
0-2 |
| CaO |
3-4.8 |
P₂O₅ |
0-2 |
| Na₂O |
1.5-3.3 |
F |
3.3-5 |
[0013] Whereas glass-ceramics satisfying the seven criteria for substrates to be used in
rigid information discs have been prepared and tested from each of the three above-described
composition families, glass-ceramics wherein canasite constitutes the predominant
crystal phase have been adjudged to be the most preferred for that application.
[0014] As is explained in Patent No. 4,971,932, the conventional rigid information disc
comprises a laminate consisting of at least three layers, viz., a substrate and a
layer of magnetic alloy joined to the substrate through an undercoat. Protective and/or
lubricating coatings are customarily applied over the layer of magnetic alloy. These
layers are collectively termed "media". Cobalt-based alloys have typically comprised
the magnetic media and a chromium film sputtered onto the substrate has commonly constituted
the underlayer. The substrate most commonly used commercially has comprised a thin
disc of aluminum metal. Prior to applying the layers of media, the aluminum substrate
must be carefully processed (including electroless NiP plating) to assure flat, non-corroding
surfaces with precisely controlled textures.
[0015] In addition to the fact that those multi-step processes incur added expense and process
control requirements, some inherent limitations of aluminum-based substrates have
led media and disc drive manufacturers to look to potential alternative substrate
materials, in particular glasses and glass-ceramics. Recognized limitations of aluminum
alloys include a tendency toward corrosion if there are any flaws in the protective
NiP coating, as well as a minimum disc thickness limitation due to the ease with which
aluminum bends because of its ductility and malleability. Alternative materials can
offer a number of advantages over aluminum-based substrates, including fewer process
steps (no NiP coatings are demanded, for example) and the ability to be mass produced
with very flat, smooth, and uniform surfaces.
[0016] The canasite-containing glass-ceramic materials referred to above in Patent No. 4,386,162
offer a unique set of properties for the substrate application. Their relatively high
elastic moduli, coupled with high body strength and toughness, permit the manufacture
and use of exceedingly thin (<0.5mm), yet rugged parts. Furthermore, their microstructures
provide an inherent tailorable surface texture. Thus, neither NiP coatings nor separate
texturizing processes are required and the substrate is reworkable, i.e., the magnetic
coatings may be removed and the disc re-processed, each of those factors involving
significant cost savings.
[0017] One problem that has been encountered with discs utilizing substrates prepared from
any glass-based materials has been the difficulty in achieving optimal magnetic performance.
Thus, coercivities of magnetic films processed in the same manner onto glass-based
discs have typically been about 10% lower than those measured on discs using NiP-plated
aluminum substrates. Laboratory investigation has demonstrated that this difference
in magnetic properties is a function of the difference in thermal properties existing
between aluminum metal and glass-based materials. That is, glass-based materials do
not achieve the same temperature as aluminum-based materials at the film deposition
station, the significance of that factor being explained below.
[0018] Extensive field experience has demonstrated that the performance of the cobalt-based
alloys, i.e., their coercivity, high frequency signal amplitude, bit shift, pulse
width, and signal-to-noise ratio thereof, is dependent upon the orientation of the
cobalt-based alloy. That orientation can be controlled through the orientation of
the chromium underlayer. It has been found that the optimum performance of the cobalt-based
alloy takes place when the texture of the chromium film is (100). [S. L. Duan et al.,
"Study of the Growth Characteristics of Sputtered Cr Thin Films",
Journal of Applied Physics,
67, (9), pp. 4913-15, May 1, 1990] The crystallographic orientation of the chromium
film, however, is dependent upon the temperature of the substrate during deposition
thereof, and, for the film thicknesses conventionally employed in underlayers, the
texture becomes predominantly (100) when the temperature of the substrate exceeds
200°C. Consequently, a substrate temperature above 200°C at the time the chromium
coating is applied comprises a prerequisite for achieving satisfactory magnetic performance
from cobalt-based alloys irrespective of the substrate composition.
[0019] In many of the conventional commercial production processes for preparing rigid information
discs, heating of the substrate is accomplished via the absorption of radiation from
a tungsten-halogen lamp in a vacuum system. Nickel phosphorus plated aluminum (NiP/Al)
substrates can be heated in this manner to temperatures in excess of 220°C in less
than about 15 seconds. Depending upon its microstructure, the amount of radiation
absorbed from such a lamp by canasite can be substantially less than that absorbed
by NiP/Al. Accordingly, in any given apparatus, canasite can require longer heating
times. In addition, cooling of the substrate which occurs during film processing/deposition
as the substrate is transferred from the heating station to the deposition station
in commercial sputtering units is greater for substrates prepared from glasses or
glass-ceramic than from NiP/Al-based substrates. And, inasmuch as media suppliers
are quite reluctant to alter their processes, in particular to processes which require
longer periods of time and, consequently, add cost, acceptance in the marketplace
of glass-based materials in the fabrication of substrates for rigid information discs
has been limited, even though they exhibit several properties superior to those found
in NiP/Al.
[0020] Therefore, the principal objective of the present invention was to develop means
for making glass-based materials capable of attaining temperatures similar to those
attained by NiP/Al during deposition of the film.
[0021] A specific objective of the present invention was to develop means for making canasite-containing
glass-ceramic substrates for rigid information discs having the capability of attaining
temperatures similar to that of NiP/Al substrates during deposition of the film and
to retain that temperature in a manner similar to NiP/Al substrates.
Summary of the Invention
[0022] Measurements of radiant energy have indicated that, at source temperatures of 1600°C
and higher, at least 90% of the energy is radiated at wavelengths shorter than 5 µm.
The silica glass envelope of the quartz-halogen lamp absorbs the remaining longer
wavelength radiation. Many glass-based materials, including glass-ceramics containing
sheet silicates or chain silicates as the predominant crystal phase, are highly absorbing
of radiant energy only at the longer wavelengths which are filtered by the silica
glass envelope. In contrast, radiant energy measurements have indicated that the NiP/Al
disc absorbs over 25% of the shorter wavelength radiation; which absorption can result
in the NiP/Al disc heating up much more rapidly than a glass-based disc.
[0023] As was remarked above, glass and glass-ceramic substrates cool more rapidly than
those fashioned from NiP/Al. It was conjectured that, if the initial temperature of
the substrate material could be increased without extending the time required for
heat up and without thermally deforming the substrate or altering the basic properties
thereof, then the faster cooling rate could be compensated for.
[0024] As a result of that conjecture, a research program was initiated to provide means
for sharply increasing the absorptance of glass-based materials and, in particular,
canasite and potassium fluorrichterite-containing glass-ceramic materials in the near
infrared portion of the radiation spectrum; viz., that portion of the spectrum having
the greatest amount of energy. The overall goal of the research program was to design
materials which would be operable in the standard process for preparing rigid information
discs, viz., to demonstrate the time and temperature parameters required in the standard
process, but without significantly affecting the basic properties of the glass-based
materials. We have accomplished that goal by incorporating closely controlled amounts
of ions which absorb radiation in the near infrared portion of the spectrum into the
glass-based compositions. The concentrations of the additives are carefully restricted
to achieve the desired absorptance without encountering thermal shock breakage of
the disc due to thermal gradients, while avoiding problems in melting and forming
the precursor glass and/or altering the crystal structure and/or the physical and
chemical characteristics of the glass or glass-ceramic material.
[0025] In our investigations discs were heated in high vacuum by means of an electrically
powered radiant heater. The rate at which the temperature of the discs is raised is
strongly dependent upon the radiant absorption and reflection spectra of the discs
and the power spectrum of the heater.
[0026] The fraction of radiant energy from the heater that is absorbed by the disc can be
calculated if the spectral absorptance, a, of the object is known. That value is determined
by measuring the spectral transmittance, t, the spectral reflectance, r, and then
incorporating those three values in the conservation of energy equation:

. For polished surfaces of NiP/Al or glass which exhibit minimal light scattering,
accurate spectrophotometric measurements of r and t are easily accomplished. The spectral
irradiance spectrum of the heater is determined from blackbody theory. A sum over
all the wavelengths of the fraction of available energy absorbed in each wavelength
interval is used to find the total absorptance by the article for a chosen source
temperature. To calculate relative cooling rates, the spectral emittance (numerically
equivalent to the spectral absorptance) is used with the blackbody temperature distribution
for the sample temperature.
[0027] Radiant energy in equilibrium with a perfectly absorbing body at a particular temperature
is known as blackbody radiation. The energy density is proportional to the fourth
power of the temperature. The wavelength distribution of energy is a continuum, with
the wavelength for the energy peak varying inversely with temperature. The product
of the temperature and peak wavelength is found to be constant. It has also been found
that 25% of the total energy always occurs at wavelengths shorter than that of the
peak. As can be appreciated, blackbody energy distribution is strictly accurate only
for materials that are perfectly absorbing at all wavelengths. For real materials
non-zero values of reflectance and/or transmittance have to be taken into account.
The variation of energy distribution with temperature becomes very important when
dealing with real materials having absorption and reflection characteristics which
are wavelength dependent.
[0028] Because, as was observed above, the silica glass envelope of the tungsten-halogen
lamp absorbs most of the infrared radiation of wavelengths longer than 5 µm, means
were sought to increase the heating rate of the canasite-containing glass-ceramic
materials by increasing the absorptance of those materials in the near infrared portion
of the radiation spectrum where most of the source energy is located. The use of transition
metal ions such as cobalt, iron, nickel, and vanadium ions as colorants and as heat
absorbing agents in glass compositions is well recognized in the glass art; see, e.g.,
U. S. Patent No. 2,938,808 (Duncan et al.), U. S. Patent No. 3,672,919 (Sack), U.
S. Patent No. 3,779,733 (Janakirama-Rao), and U. S. Patent No. 3,966,447 (Asahara
et al.). The ferrous ion has been utilized extensively in the glass art because it
supplies a strong, broad band absorption in the near infrared portion of the radiation
spectrum.
[0029] The transition metal ions have likewise been utilized in colorants in glass-ceramic
articles; see for example, U. S. Patent No. 4,007,048 (Sack et al.), U. S. Patent
No. 4,461,839 (Rittler), U. S. Patent No. 4,192,688 (Babcock et al.) and U. S. Patent
No. 5,070,044 (Pinckney). However, unlike glass bodies wherein the ions are essentially
uniformly dispersed throughout, the place assemblage of a glass-ceramic can result
in particular ions being present in the crystal phase and/or in the glass phase, with
the behavior of the ions being influenced by their site in either the crystal phase
or the glass phase. For example, ions constituting part of a crystal lattice can be
constrained from exhibiting the behavior demonstrated when present in a glass. Accordingly,
because of the likelihood of transition metal ions entering into the structure of
canasite [Ca₅Na₄K₂(Si₁₂O₃₀)F₄] with probable solid solution to [Ca₅Na₃K₃(Si₁₂O₃₀)F₄]
or into the structure of potassium fluorrichterite KNaCaMg₅Si₈O₂₂F₂, its effectiveness
in absorbing infrared radiation, particularly in the near infrared portion of the
radiation spectrum, was in doubt. That is, would such large additions of transition
metal ions be required to achieve the required deposition temperature that the physical
properties of the canasite- and potassium fluorrichterite-containing glass-ceramics
would be unduly modified? Or, would such large additions of transition metal ions
be required that melting of the batch for the precursor glass be deleteriously affected?
[0030] In addition, and contrary to the situation with respect to NiP/Al or glass bodies,
measurements of infrared reflectance and transmittance made on glass-ceramic articles
are difficult to use in calculating comparative heating and cooling. This difficulty
results from light scattering taking place because of the microstructure present in
the latter articles, which microstructure consists of crystals dispersed in a residual
glassy matrix, the crystals constituting the greater proportion of the glass-ceramic
articles.
[0031] To circumvent the difficulties and complications faced in measuring and analyzing
infrared reflectance and transmittance of glass-ceramic articles, experiments were
conducted wherein comparative heating and cooling responses of NiP/Al and glass-ceramics
were determined in a high vacuum. The heat source consisted of two 500 watt tungsten
halogen lamps whose radiation was incident on one side of the sample. The thermometer
comprised a remote sensing thermocouple of suitable design.
[0032] Laboratory investigations have determined that the incorporation of no more than
about 0.05% by weight total of at least one metal oxide selected from the group consisting
of cobalt oxide, iron oxide, and nickel oxide to glass-based materials boosts the
energy absorptance of those materials to such a degree that rigid information discs
for memory storage devices utilizing those materials as substrates therefor can be
heated rapidly to temperatures in excess of 220°C. Indeed, those materials heat up
more rapidly than NiP/Al materials. In general, minimum levels of dopant ranging about
0.1-0.2% will be incorporated into the glass composition to assure the desired rapid
heat up. Much greater total concentrations of dopant(s) can be included, e.g., 2%
or more, but with no substantive advantages flowing therefrom. Moreover, high levels
of dopant may lead to problems in melting the glass and adverse effects upon the properties
of the glass-based materials. Therefore, an upper limit of 2% has been deemed to constitute
a practical maximum with additions of 0.2-0.5% being preferred.
Brief Description of the Drawing
[0033] The appended drawing presents curves illustrating the rates of heat up of the inventive
materials and NiP/Al materials when exposed to a heat source comprising two 500 watt
tungsten halogen lamps whose radiation was incident on one side of the sample.
Description of Preferred Embodiments
[0034] Because the most preferred embodiment of the present invention consists of substrates
for rigid information discs used in memory storage devices prepared from glass-ceramic
materials wherein canasite constitutes the predominant crystal phase and iron oxide
and/or nickel oxide and/or cobalt oxide comprise the infrared radiation absorbing
agent, the following description will be concentrated on compositions designed to
produce such materials. Nevertheless, operable glass compositions in the soda lime
silicate field, the alkali metal aluminosilicate field, and the alkali metal borosilicate
field are also provided.
[0035] TABLE I records a number of glass compositions, expressed in terms of parts by weight
on the oxide basis, illustrating the present invention. Because it is not known with
which cation(s) the fluoride is combined, it is merely reported as fluoride and the
fluoride ≎ oxygen correction factor supplied for the base composition therefor. The
Fe₃O₄, Co₃O₄, and NiO were added in addition to the base glass composition. Furthermore,
because the sum of the individual components of the recited compositions totals or
closely approximates 100, for all practical purposes the tabulated values may be considered
to represent weight percent. The batch ingredients, themselves, may comprise any materials,
either the oxides or other compounds, which, when melted together, will be converted
into the desired oxide in the proper proportions. For example, Na₂CO₃ may provide
the source of Na₂O and the minerals limestone and aragonite may comprise sources of
CaO. The aragonite employed in the following examples contained a small amount (<0.1%)
sulfur trioxide as an impurity. To determine the effect of redox conditions, in certain
examples part of the Na₂O content was added in the form of NaNO₃ in a proportion of
27 parts/1000 parts batch to achieve an oxidizing environment during melting. Where
that proportion of NaNO₃ was incorporated, the Na₂O content is designated with a N.
Where aragonite constituted the source of CaO, the CaO content is designated with
an A; where limestone formed the source of CaO, the CaO concentration is designated
with a L. To assure reducing conditions during melting, sucrose was added to several
of the batches. In each example where present, the iron oxide, nickel oxide, and cobalt
oxide, the NaNO₃, and the sugar were added in addition to the base glass composition.
Sb₂O₃ performed its customary function as a fining agent.
[0036] The batch constituents were compounded, ballmilled together to aid in obtaining a
homogeneous melt, and charged into platinum crucibles. Lids were placed upon the crucibles
and the crucibles were moved into a furnace operating at about 1325°C. After about
three hours the crucibles were withdrawn from the furnace, the melts were poured onto
a steel plate, and the resulting glass slabs were transferred immediately to an annealer
operating at about 500°C.
[0037] Samples having dimensions of about 2" X 2" X 0.25" (∼5.1 X 5.1 X 0.6 cm) were prepared
from each annealed slab and introduced into an electrically heated furnace and subjected
to the following heat treatment (unless otherwise specified):
Room temperature to 850°C at 300°C/hour;
Hold at 850°C for 1 hour;
Cool to room temperature at furnace rate.
The resulting glass-ceramic bodies were highly crystalline with canasite (average
size in longest dimension of about 5 µm) constituting essentially the sole crystal
phase.
[0038] The base glass composition is reported below in terms of weight percent:
| SiO₂ |
57.3 |
| CaO |
20.2 |
| Na₂O |
8.0 |
| K₂O |
8.8 |
| Al₂O₃ |
2.0 |
| F |
6.3 |
| |

|
| F≎O |
-2.6 |
| |

|
[0039] Table I below reports additions of Fe₃O₄, Fe₂O₃, Co₃O₄, and NiO along with notations
of whether a portion of the Na₂O content comprised NaNO₃, whether sucrose was added,
and whether aragonite or limestone provided the source of CaO. The table also records
the transmittances of the precursor glasses and the crystallized glass-ceramics at
wavelengths of 1100 and 1800 nm, respectively, as measured on samples with polished
surfaces having the dimensions of 1" X 1" X 1 mm (∼25.4 x 25.4 X 1 mm).

*Crystallized according to the following heat treatment schedule:
Room temperature to 680°C at 300°C/hour;
Hold at 680°C for 1 hour;
680°C to 720°C at 300°C/hour;
Hold at 720°C for 2 hours; and
Cool to room temperature at furnace rate to yield highly crystalline articles of
relatively fine-grained crystal (average size is longest dimension of about 1 µm).
[0040] As is immediately evident from a review of Table I, absorption is much greater where
the melting conditions are mildly reducing, rather than oxidizing.
[0041] Radiation-induced heat-up rates in vacuum were determined on a number of the examples
of Table I and those results are graphically depicted in the appended drawing. The
heating source contained within a glass bell jar was a bank of two 500 watt tungsten
halogen lamps whose radiation was incident on one side of the samples. The measurement
consisted of the time required to heat the samples from room temperature to about
280°C. The sample temperatures were measured utilizing an Omega OS36 Series Infrared
Thermocouple. This non-contact device has a 130° field of view for target distances
up to 0.5" (∼1.3 cm), a spectral response from 6.5-14 µm, and a response time of 80
ms. The temperature range for the unit used, viz., an OS36-J-440F, was 170°-250°C
(±2%) or 140°-280°C (± 5%). The samples were held at one corner via an insulated clamp
and were centered over and at a distance of 4.9 cm above the two tungsten halogen
lamps. The infrared thermocouple was positioned a distance of 0.3 cm behind the samples
and, hence, read the back surface temperature of the sample. A shutter interposed
between the samples and the lamps allowed the lamps to reach their equilibrium temperature
prior to the samples being actually exposed to the radiation. The pressure in the
chamber during the measurements was about 40 µm of Hg. The results of those determinations
are reported in the appended drawing along with measurements of a sample of NiP/Al.
In each instance the precursor glass article had been crystallized to a glass-ceramic
through one of the following heat treatment procedures:
Heat Treatment 1
[0042] Room temperature to 600°C at 300°C/hour;
Hold at 600°C for 1 hour;
600° to 850°C at 300°C/hour;
Hold at 850°C for 2 hours; and
Cool at room temperature at furnace rate to yield a glass-ceramic body containing
canasite as the predominant crystal phase.
or
Heat Treatment 2
[0043] Room temperature to 680°C at 300°C/hour;
Hold at 680°C for 1 hour;
680°C to 720°C at 300°C/hour;
Hold at 720°C for 2 hours; and
Cool to room temperature at furnace rate to yield a relatively fine-grained glass-ceramic
body containing canasite as the predominant crystal phase.
[0044] The drawing graphically records the time in seconds for the samples to reach at least
280°C. The measurements were begun at about 170°C. Curve A designates the base glass;
curve B the base glass crystallized to a glass-ceramic utilizing Heat Treatment 1;
and curve C the base glass crystallized to a glass-ceramic employing Heat Treatment
2; all samples being free of Co₃O₄, Fe₂O₃, or NiO. Curve D designates the NiP/Al material.
Curve E designates Example 10 crystallized in accordance with Heat Treatment 1. Curve
F designates Example 13 crystallized in accordance with Heat Treatment 1. Curve G
designates Example 6 crystallized in accordance with Heat Treatment 2. Curve H designates
Example 3 crystallized in accordance with Heat Treatment 1. Curve I designates Example
12 crystallized in accordance with Heat Treatment 1. Curve J designates Example 6
crystallized in accordance with Heat Treatment 1. Curve K designates Example 7 crystallized
in accordance with Heat Treatment 1.
[0045] An inspection of the drawing immediately evidences that, depending upon the crystal
size, which, in turn, is dependent upon the crystallizing procedure, the undoped glass-ceramic
can heat up at about the same rate as NiP/Al, whereas the samples doped with iron
and/or nickel can heat up more than twice as rapidly as NiP/Al, particularly in those
instances where the melting of the precursor glass was carried out under reducing
rather than oxidizing conditions (compare Examples 10 and 13).
[0046] The laboratory apparatus for measuring the rate of cooling of the sample was similar
to that described above for conducting the heat-up determinations, except that the
samples were heated to about 270°C and the shutter then closed to isolate the samples
from the lamps. That practice resulted in one side of the samples seeing an aluminum
shutter at a temperature of about 50°C with the other side seeing a glass bell jar
at a temperature of about 20°C during the cooling. Cooling data are illustrated in
FIGURE 2. As can be observed therefrom, the doped glass-ceramic samples cool up to
about twice as rapidly as NiP/Al. Nevertheless, because the glass-ceramic materials
can be safely heated to temperatures much higher than NiP/Al, the temperature at film
deposition can be matched with that of NiP/Al.
[0047] Table II reports a base glass composition, expressed in terms of weight percent on
the oxide basis, illustrative of glasses in the soda lime silica (SLS) system; a base
glass composition, expressed in terms of weight percent on the oxide basis, illustrative
of glasses in the alkali metal aluminosilicate (AAS) system; and a base glass composition,
expressed in terms of weight percent on the oxide basis, illustrative of glasses in
the alkali metal borosilicate (ABS) system. Compounding, mixing, and melting of the
glass batches in platinum crucibles were conducted in like as outlined above with
respect to the glasses recorded in Table I. The soda lime silica glass batches were
melted for 4 hours at 1550°C and the resulting slabs annealed at 600°C. The alkali
metal aluminosilicate glasses were melted for 8 hours at 1625°C and annealed at 650°C.
The alkali metal borosilicate glasses were melted for 8 hours at 1625°C and annealed
at 600°C. Aragonite was not used as a batch material nor was NaNO₃. Sucrose in an
amount of 0.5% by weight was included in each batch to assure reducing conditions.
TABLE II
| |
SLS |
AAS |
ABS |
| SiO₂ |
71.0 |
63.0 |
72.0 |
| Al₂O₃ |
1.5 |
14.0 |
4.5 |
| Na₂O |
13.0 |
14.0 |
6.0 |
| K₂O |
1.0 |
-- |
0.5 |
| CaO |
9.5 |
-- |
0.5 |
| MgO |
4.0 |
-- |
-- |
| Li₂O |
-- |
5.0 |
-- |
| ZrO₂ |
-- |
4.0 |
-- |
| B₂O₃ |
-- |
-- |
10.0 |
| ZnO |
-- |
-- |
3.0 |
| BaO |
-- |
-- |
3.5 |
[0048] TABLE III records additions of Fe₂O₃, NiO, and Co₃O₄ in weight percent. 1% by weight
As₂O₃ was included in the alkali metal aluminosilicate (AAS) glasses and the alkali
metal borosilicate (ABS) glasses as a fining agent. Table III also recites the transmittances
of the glasses at wavelengths of 1100 nm and 1800 nm, respectively, as measured on
samples with polished surfaces having the dimensions of 1" X 1" X 1 mm (∼25.4 X 25.4
X 1 mm).
TABLE III
| |
SLS 19 |
SLS 20 |
SLS 21 |
SLS 22 |
SLS 23 |
| Fe₂O₃ |
-- |
0.5 |
1.2 |
-- |
-- |
| NiO |
-- |
-- |
-- |
0.2 |
00 |
| Co₃O₄ |
-- |
-- |
-- |
-- |
0.5 |
| As₂O₃ |
-- |
-- |
-- |
-- |
-- |
| 1100 |
89 |
39 |
13 |
44 |
84 |
| 1800 |
91 |
64 |
40 |
72 |
83 |
| |
AAS 24 |
AAS 25 |
AAS 26 |
AAS 27 |
AAS 28 |
| Fe₂O₃ |
-- |
0.5 |
1.2 |
-- |
-- |
| NiO |
-- |
-- |
-- |
0.1 |
-- |
| Co₃O₄ |
-- |
-- |
-- |
-- |
0.05 |
| As₂O₃ |
1.0 |
1.0 |
1.0 |
1.0 |
1.0 |
| 1100 |
93 |
66 |
40 |
87 |
89 |
| 1800 |
93 |
81 |
66 |
88 |
85 |
| |
ABS 29 |
ABS 30 |
ABS 31 |
ABS 32 |
ABS 33 |
| Fe₂O₃ |
-- |
0.5 |
1.2 |
-- |
-- |
| NiO |
-- |
-- |
-- |
0.2 |
-- |
| Co₃O₄ |
-- |
-- |
-- |
-- |
0.05 |
| As₂O₃ |
1.0 |
1.0 |
1.0 |
1.0 |
1.0 |
| 1100 |
91 |
49 |
21 |
39 |
82 |
| 1800 |
91 |
68 |
48 |
68 |
81 |
[0049] As can be observed from an inspection of Tables II and III, additions of iron oxide,
nickel oxide, and cobalt oxide boost the energy absorptance of the glasses.
1. A rigid information disc for use in a magnetic memory storage device comprising a
substrate having a layer of magnetic media joined to the surface of said substrate
through an underlayer wherein said substrate consists of a glass-based material, the
improvement which comprises including 0.05-2% by weight total of at least one member
of the group consisting of cobalt oxide, iron oxide, and nickel oxide in the composition
of said glass-based material.
2. A rigid information disc according to claim 1 wherein said glass-based material consists
of a glass-ceramic wherein crystals exhibiting a chain silicate structure or a sheet
silicate structure comprise the predominant crystal phase.
3. A rigid information disc according to claim 1 wherein said crystals exhibit a chain
silicate structure and are selected from the group consisting of predominantly canasite,
predominantly potassium fluorrichterite, and predominantly potassium fluorrichterite,
but also containing a substantial amount of cristobalite.
4. A rigid information disc according to claim 3 wherein said crystals consist predominantly
of canasite and have a composition consisting essentially, expressed in terms of weight
percent on the oxide basis, of
| SiO₂ |
50-70 |
MgO |
0-2 |
| CaO |
15-25 |
ZnO |
0-2 |
| Na₂O |
6-10 |
SnO₂ |
0-2 |
| K₂O |
6-12 |
Sb₂O₃ |
0-1 |
| Al₂O₃ |
1-4 |
F |
4-9 . |
5. A rigid information disc according to claim 3 wherein said crystals consist predominantly
of potassium fluorrichterite and has a composition consisting essentially, expressed
in terms of weight percent on the oxide basis, of
| SiO₂ |
58-70 |
K₂O |
3.8-7 |
| Al₂O₃ |
0.5-3 |
Li₂O |
0.5-2 |
| MgO |
13-17.5 |
BaO |
0-2.5 |
| CaO |
3-7 |
P₂O₅ |
0-2.5 |
| Na₂O |
1.5-4 |
F |
3-5.5 . |
6. A rigid information disc according to claim 3 wherein said crystals consist predominantly
of potassium fluorrichterite, but also consist of a substantial amount of cristobalite,
and have a composition consisting essentially, expressed in terms of weight percent
on the oxide basis, of
| SiO₂ |
65-69 |
K₂O |
4.2-6 |
| Al₂O₃ |
0.75-3 |
Li₂O |
0.5-2 |
| MgO |
13.5-16.5 |
BaO |
0-2 |
| CaO |
3-4.8 |
P₂O₅ |
0-2 |
| Na₂O |
1.5-3.3 |
F |
3.3-5 . |
7. A rigid information disc according to any one of claims 1-7 wherein said crystals
exhibit a sheet silicate structure and are selected from the group consisting of predominantly
fluorophlogopite solid solution and predominantly tetrasilicic fluormica.
8. A rigid information disc according to any one of claims 1-7 wherein said crystals
consist predominantly of fluorophlogopite solid solution and have a composition consisting
essentially, expressed in terms of weight percent on the oxide basis, of
| SiO₂ |
25-60 |
Cs₂O |
0-20 |
| B₂O₃ |
5-15 |
Na₂O+K₂O+Rb₂O+Cs₂O |
2-20 |
| Al₂O₃ |
5-25 |
MgO |
4-25 |
| B₂O₃+Al₂O₃ |
15-35 |
Li₂O |
0-7 |
| Na₂O |
0-15 |
MgO+Li₂O |
6-25 |
| K₂O |
0-15 |
F |
4-20 . |
9. A rigid information disc according to claim 8 wherein said crystals consist predominantly
of tetrasilicic fluormica and have a composition consisting essentially, expressed
in terms of weight percent on the oxide basis, of 45-70% SiO₂, 8-20% MgO, 8-15% MgF₂,
5-25% R₂O, wherein R₂O consists of 0-20% K₂O, 0-20% Rb₂O, and 0-20% Cs₂O, 0-20% RO,
wherein RO consists of 0-20% SrO, 0-20% BaO, and 0-20% CdO, and 5-35% R₂O+RO.
10. A rigid information disc according to claim 8 wherein said glass-based material consists
of a glass having a base composition selected from the group of glasses within the
soda lime silica system, glasses within the alkali metal aluminosilicate system, and
glasses within the alkali metal borosilicate system.
11. A rigid information disc according to any one of claims 1-10 wherein said glass-based
material contains 0.2-0.5% total of at least one member of the group consisting of
cobalt oxide, iron oxide, and nickel oxide.
12. Use of the rigid information disc according to any one of the preceding claims in
a magnetic memory storage device comprising said disc and a head pad.